CN101328103B - Method for converting methanol or dimethyl ether into low carbon alkene - Google Patents
Method for converting methanol or dimethyl ether into low carbon alkene Download PDFInfo
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- CN101328103B CN101328103B CN2008100434876A CN200810043487A CN101328103B CN 101328103 B CN101328103 B CN 101328103B CN 2008100434876 A CN2008100434876 A CN 2008100434876A CN 200810043487 A CN200810043487 A CN 200810043487A CN 101328103 B CN101328103 B CN 101328103B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
The invention relates to a method for converting methanol or dimethyl ether into light olefins, mainly solves the problem of high cost caused by low yield of the light olefins, low treatment performance of the reactor and large dosage of catalyst. The method comprises contacting an aluminosilicophosphate molecular sieve catalyst with materials containing methanol or dimethyl ether in the reaction zone of a fluidized bed reactor, converting the methanol or dimethyl ether into the product containing ethylene and propylene under a reaction pressure (gauge pressure) of 0.05-1MPa, an average temperature in the reaction zone of 450-550 DEG C and an average superficial gas velocity in the reaction zone of 0.8-2.0m/s, wherein the average density of the reaction zone is 20-300kg/cm<3>, the catalyst average coke content in the reaction zone is 1.5-4.5wt%. The technique scheme of the invention well solves the above problem and is suitable to the industrial production of light olefins.
Description
Technical field
The present invention relates to the method that a kind of methyl alcohol or dimethyl ether conversion are low-carbon alkene.
Background technology
Low-carbon alkene mainly is ethene and propylene, is two kinds of important basic chemical industry raw materials, and its demand is in continuous increase.Usually, ethene, propylene are to produce through petroleum path, but because limited supply of petroleum resources and higher price, the cost of being produced ethene, propylene by petroleum resources constantly increases.In recent years, people begin to greatly develop the technology that alternative materials transforms system ethene, propylene.Wherein, One type of important alternative materials that is used for low-carbon alkene production is an oxygenatedchemicals; For example alcohols (methyl alcohol, ethanol), ethers (dme, methyl ethyl ether), ester class (methylcarbonate, methyl-formiate) etc., these oxygenatedchemicalss can be transformed through coal, Sweet natural gas, biomass equal energy source.Some oxygenatedchemicals can reach fairly large production, like methyl alcohol, can be made by coal or Sweet natural gas, and technology is very ripe, can realize up to a million tonnes industrial scale.Because the popularity in oxygenatedchemicals source is added and is transformed the economy that generates low-carbon alkene technology, so by the technology of oxygen-containing compound conversion to produce olefine (OTO), particularly the technology by methanol conversion system alkene (MTO) receives increasing attention.
In US 4499327 patents silicoaluminophosphamolecular molecular sieves catalyst applications is studied in great detail in methanol conversion system olefin process, think that SAPO-34 is the first-selected catalyzer of MTO technology.The SAPO-34 catalyzer has very high selectivity of light olefin, and activity is also higher, and can make methanol conversion is the degree that was less than in reaction times of low-carbon alkene 10 seconds, more even reach in the reaction time range of riser tube.
Announced among the US 6166282 that a kind of oxygenate conversion is the technology and the reactor drum of low-carbon alkene; Adopt fast fluidized bed reactor; Gas phase is after the lower Mi Xiangfanyingqu reaction of gas speed is accomplished; After rising to the fast subregion that internal diameter diminishes rapidly, adopt special gas-solid separation equipment initial gross separation to go out most entrained catalyst.Because reaction after product gas and catalyzer sharp separation have effectively prevented the generation of secondary reaction.
Catalyst levels is all bigger in the prior art, and to guarantee that catalyzer has enough activity to transform raw material in the reaction zone, but higher owing to required catalyst production cost, this must increase the running cost of whole technology.The present invention adopts lower reaction zone density under condition for validity, to realize higher feed stock conversion and selectivity of light olefin, has solved this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention is that the yield of light olefins that exists in the prior art is low, the reactor for treatment ability is lower, than problems such as height, it is the method for low-carbon alkene that a kind of new methyl alcohol or dimethyl ether conversion are provided to catalyst levels than the cost that causes greatly.This method is used for the production of low-carbon alkene, has that catalyst levels is few, the reactor for treatment ability is big, yield of light olefins advantage of higher in the product.
For solving the problems of the technologies described above; The technical scheme that the present invention adopts is following: a kind of methyl alcohol or dimethyl ether conversion are the method for low-carbon alkene; The raw material that comprises methyl alcohol or dme gets in the reaction zone of fluidized-bed reactor; Contact with the catalyzer that comprises silicoaluminophosphamolecular molecular sieve; Counting 0.05～1MPa, reaction zone medial temperature with gauge pressure in reaction pressure is that 450～550 ℃, the average empty tower gas velocity of reaction zone are under the condition of 0.8～2.0 meter per second, is the product that comprises ethene, propylene with methyl alcohol or dimethyl ether conversion; Wherein, the mean density of said reaction zone is 20～300 kilograms per cubic meter, and the average coke content of catalyzer in the said reaction zone is 1.5～4.5% weight.
In the technique scheme, said silicoaluminophosphamolecular molecular sieve is selected from least a among SAPO-18, the SAPO-34, and preferred version is selected from SAPO-34; Said fluidized-bed reactor is turbulent fluidized bed or fast fluidized bed, and preferred version is selected from fast fluidized bed; Said reaction pressure is that 0.1～0.3MPa, reaction zone medial temperature preferable range are that mean density preferable range that 460～500 ℃, the average empty tower gas velocity preferable range of reaction zone are 1.0～1.6 meter per seconds, reaction zone is that the average coke content preferable range of catalyzer in 50～120 kilograms per cubic meter, the reaction zone is 2.0～3.0% weight in the gauge pressure preferable range.
The method of calculation of coke content according to the invention are that carbon deposit quality on the catalyzer of certain mass is divided by described catalyst quality.Carbon deposit measuring method on the catalyzer is following: will mix the catalyst mix that has carbon deposit comparatively uniformly; The accurate carbon-bearing catalyzer of weighing certain mass then; Be put in the pyrocarbon analyser and burn; Through the carbonic acid gas quality of infrared analysis burning generation, thereby obtain the carbonaceous amount on the catalyzer.
The method of calculation of reaction zone mean density according to the invention are that the gross weight of reaction zone inner catalyst is divided by the reaction zone volume.
Adopt method of the present invention, have following advantage: (1) reaction pressure is higher, and the reaction zone linear speed is high, and the reaction zone processing power is high; (2) adopt fast fluidized bed reactor, and the high linear speed operation, the raw material processing power of unit bed volume is big, and for molecular weight less methyl alcohol or dme raw material, required reactor volume is less, and the difficulty that industry is amplified is low; (3) adopt the bed density operation of low reaction district, the raw material processing power of unit catalyzer is big, perhaps reaches identical raw material processing power, and required catalyst levels is little, thereby has reduced the production cost of technology; (4) under higher pressure, lower bed density, higher linear speed, can obtain higher transformation efficiency and selectivity of light olefin equally.
Adopt technical scheme of the present invention: said silicoaluminophosphamolecular molecular sieve is selected from least a among SAPO-18, the SAPO-34; Said fluidized-bed reactor is turbulent fluidized bed or fast fluidized bed; It is that 450～550 ℃, the average empty tower gas velocity of reaction zone are that the mean density of 0.8～2.0 meter per second, reaction zone is that the average coke content of catalyzer in 20～300 kilograms per cubic meter, the reaction zone is 1.5～4.5% weight that reaction pressure is counted 0.05～1MPa, reaction zone medial temperature with gauge pressure; Methyl alcohol or dimethyl ether conversion rate are up to 99.88% weight; Low-carbon alkene carbon back selectivity is up to 81.51% weight, has obtained better technical effect.
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
In small-sized fast fluidized bed reaction device, be raw material with pure methyl alcohol, the reaction zone medial temperature is 500 ℃; Reaction pressure is counted 0.1MPa with gauge pressure, and catalyzer adopts SAPO-34, and the average void tower linear speed of reaction zone is 1.6 meter per seconds; The average coke content of reaction zone is 2.0% weight, and the reaction zone mean density is 50 kilograms per cubic meter, and the reactor outlet product adopts online gas chromatographic analysis; Calculation result is: methanol conversion is 99.14% weight, and low-carbon alkene carbon back selectivity is 81.24% weight.
[embodiment 2]
In small-sized fast fluidized bed reaction device, be raw material with pure methyl alcohol, the reaction zone medial temperature is 550 ℃; Reaction pressure is counted 0.3MPa with gauge pressure, and catalyzer adopts SAPO-34, and the average void tower linear speed of reaction zone is 1.0 meter per seconds; The average coke content of reaction zone is 1.5% weight, and the reaction zone mean density is 120 kilograms per cubic meter, and the reactor outlet product adopts online gas chromatographic analysis; Calculation result is: methanol conversion is 99.33% weight, and low-carbon alkene carbon back selectivity is 80.86% weight.
[embodiment 3]
In small-sized fast fluidized bed reaction device, be raw material with pure methyl alcohol, the reaction zone medial temperature is 450 ℃; Reaction pressure is counted 0.05MPa with gauge pressure, and catalyzer adopts SAPO-34, and the average void tower linear speed of reaction zone is 2.0 meter per seconds; The average coke content of reaction zone is 3.0% weight, and the reaction zone mean density is 50 kilograms per cubic meter, and the reactor outlet product adopts online gas chromatographic analysis; Calculation result is: methanol conversion is 98.64% weight, and low-carbon alkene carbon back selectivity is 81.51% weight.
[embodiment 4]
In small-sized turbulent fluidized bed reaction unit, be raw material with the pure Dimethyl ether, the reaction zone medial temperature is 550 ℃; Reaction pressure is counted 0.1MPa with gauge pressure; Catalyzer adopts SAPO-34, and the average void tower linear speed of reaction zone is 0.8 meter per second, and the average coke content of reaction zone is 1.5% weight; The reaction zone mean density is 300 kilograms per cubic meter; The reactor outlet product adopts online gas chromatographic analysis, and calculation result is: the dimethyl ether conversion rate is 99.88% weight, and low-carbon alkene carbon back selectivity is 80.77% weight.
[embodiment 5]
In small-sized fast fluidized bed reaction device, be raw material with methyl alcohol and dme, the weight ratio of methyl alcohol and dme is 5: 1; The reaction zone medial temperature is 460 ℃, and reaction pressure is counted 0.3MPa with gauge pressure, and catalyzer adopts SAPO-18; The average void tower linear speed of reaction zone is 2.0 meter per seconds; The average coke content of reaction zone is 3.0% weight, and the reaction zone mean density is 20 kilograms per cubic meter, and the reactor outlet product adopts online gas chromatographic analysis; Calculation result is: methyl alcohol and dme total conversion rate are 97.94% weight, and low-carbon alkene carbon back selectivity is 79.64% weight.
[embodiment 6]
In small-sized fast fluidized bed reaction device, be raw material with methyl alcohol, the reaction zone medial temperature is 550 ℃; Reaction pressure is counted 1MPa with gauge pressure, and catalyzer adopts SAPO-34, and the average void tower linear speed of reaction zone is 0.8 meter per second; The average coke content of reaction zone is 1.5% weight, and the reaction zone mean density is 300 kilograms per cubic meter, and the reactor outlet product adopts online gas chromatographic analysis; Calculation result is: the methyl alcohol total conversion rate is 95.28% weight, and low-carbon alkene carbon back selectivity is 78.42% weight.
[comparative example 1]
In small-sized fast fluidized bed reaction device, be raw material with methyl alcohol, the reaction zone medial temperature is 500 ℃; Reaction pressure is counted 0.1MPa with gauge pressure, and catalyzer adopts SAPO-34, and the average void tower linear speed of reaction zone is 0.5 meter per second; The average coke content of reaction zone is 3.5% weight, and the reaction zone mean density is 624 kilograms per cubic meter, and the reactor outlet product adopts online gas chromatographic analysis; Calculation result is: the methyl alcohol total conversion rate is 99.78% weight, and low-carbon alkene carbon back selectivity is 76.20% weight.
Obviously, adopt technical scheme of the present invention, under the condition that guarantees the methyl alcohol high conversion, can realize higher low-carbon alkene carbon back selectivity, have tangible technical superiority, can be applied in the industrial production of low-carbon alkene.
Claims (4)
1. methyl alcohol or dimethyl ether conversion are the method for low-carbon alkene; The raw material that comprises methyl alcohol or dme gets in the reaction zone of fluidized-bed reactor; Contact with the catalyzer that comprises silicoaluminophosphamolecular molecular sieve; Counting 0.05～1MPa, reaction zone medial temperature with gauge pressure in reaction pressure is that 450～550 ℃, the average empty tower gas velocity of reaction zone are under the condition of 0.8～2.0 meter per second, is the product that comprises ethene, propylene with methyl alcohol or dimethyl ether conversion; Wherein, the mean density of said reaction zone is 20～300 kilograms per cubic meter, and the average coke content of catalyzer in the said reaction zone is 1.5～4.5% weight; Wherein, said silicoaluminophosphamolecular molecular sieve is selected from least a among SAPO-18, the SAPO-34.
2. be the method for low-carbon alkene according to said methyl alcohol of claim 1 or dimethyl ether conversion, it is characterized in that said fluidized-bed reactor is turbulent fluidized bed or fast fluidized bed.
3. be the method for low-carbon alkene according to said methyl alcohol of claim 2 or dimethyl ether conversion, it is characterized in that said silicoaluminophosphamolecular molecular sieve is selected from SAPO-34; Said fluidized-bed reactor is a fast fluidized bed.
4. be the method for low-carbon alkene according to said methyl alcohol of claim 1 or dimethyl ether conversion, it is characterized in that it is that 460～500 ℃, the average empty tower gas velocity of reaction zone are 1.0～1.6 meter per seconds that said reaction pressure is counted 0.1～0.3MPa, reaction zone medial temperature with gauge pressure; The mean density of said reaction zone is 50～120 kilograms per cubic meter, and the average coke content of catalyzer in the said reaction zone is 2.0～3.0% weight.
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| CN2008100434876A CN101328103B (en) | 2008-06-12 | 2008-06-12 | Method for converting methanol or dimethyl ether into low carbon alkene |
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| CN2008100434876A CN101328103B (en) | 2008-06-12 | 2008-06-12 | Method for converting methanol or dimethyl ether into low carbon alkene |
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| CN101328103B true CN101328103B (en) | 2012-06-27 |
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| CN102372539A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for producing low-carbon olefin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4499327A (en) * | 1982-10-04 | 1985-02-12 | Union Carbide Corporation | Production of light olefins |
| US6166282A (en) * | 1999-08-20 | 2000-12-26 | Uop Llc | Fast-fluidized bed reactor for MTO process |
| CN101165018A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Method for producing ethylene and propylene |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4499327A (en) * | 1982-10-04 | 1985-02-12 | Union Carbide Corporation | Production of light olefins |
| US6166282A (en) * | 1999-08-20 | 2000-12-26 | Uop Llc | Fast-fluidized bed reactor for MTO process |
| CN101165018A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Method for producing ethylene and propylene |
Non-Patent Citations (3)
| Title |
|---|
| 刘红星 等.甲醇制烯烃(MTO)研究新进展.《天然气化工》.2002,第27卷(第3期),49-56. * |
| 白尔铮.甲醇制烯烃用SAPO-34催化剂新进展.《工业催化》.2001,第9卷(第4期),3-8. * |
| 齐国祯 等.甲醇制低碳烯烃(MTO)反应热力学研究.《石油与天然气化工》.2005,第34卷(第5期),349-353. * |
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